Electrocatalytic reduction of protons to hydrogen by a copper complex of the pentadentate ligand Dmphen-DPA in a nonaqueous electrolyte
| Autor: | Ying-Chun Gao, Yan Meng, Xiao-Wei Song, Changneng Chen, Rong-Yi Huang, Wenjing Wang, Jun-Wei Wang, Ying-Guo Zhao |
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| Rok vydání: | 2019 |
| Předmět: |
Ligand
chemistry.chemical_element Protonation 02 engineering and technology General Chemistry Electrolyte 010402 general chemistry 021001 nanoscience & nanotechnology Electrochemistry 01 natural sciences Copper Catalysis Reductive elimination 0104 chemical sciences chemistry.chemical_compound chemistry Polymer chemistry Materials Chemistry Amine gas treating 0210 nano-technology Acetonitrile |
| Zdroj: | New Journal of Chemistry. 43:18134-18140 |
| ISSN: | 1369-9261 1144-0546 |
| DOI: | 10.1039/c9nj04275j |
| Popis: | A copper complex based on the pentadentate aminopyridine ligand [(9-methyl-1,10-phenanthrolin-2-yl)methyl]bis-(pyridin-2-ylmethyl)amine (Dmphen-DPA), namely [Cu(Dmphen-DPA)](ClO4)2 (1), was synthesized and characterized by elemental analysis, HR-MS spectroscopy and X-ray single crystal diffraction. The complex has five-coordinated solid-state structures, but has an open coordination site in acetonitrile. The electrochemical studies reveal that complex 1 has an electrocatalytic proton reduction activity in acetonitrile, when using acetic acid as a proton source with icat/ip ∼ 2.5. DFT calculations suggest that the parent copper complex undergoes two successive reductions to generate the radical species [Cu(I)(Dmphen-DPA˙−)]0, which is protonated at the low-valence copper center to afford a reactive CuII–H intermediate. The CuII–H species combines bimolecularly and generates H2via reductive elimination. |
| Databáze: | OpenAIRE |
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